Process for desulphuring unsaturate and waste oils and their conversion into saturate hydrocarbons



Dec. 14 1926.

J. A. BISHOP PRocEss FOR DESULPHURING UNSATURATE AND wAsTE oILs AND THEIR CONVERSION INTO SATURATE HYDROCARBONS .Filed April 9.11923 '30 or to Patented Dec. 14, 1926.

UNITED 'STATES' PATENT OFFICE.

JAMES A. BISHOP, oEnENvEn, coLonaDo.

Pnocnss non vnl:sULPHURrNe UNsa'rUnA'rn Aim wAsTE'oILs ANnzrHEm coNvEnsIoN INT sA'rURA'rn HYDaocanBoNs.

Application mea Mirna,

This invention has to do with an improved processfor the distillation of oils and oil bearing materials, and also has to do with an improved process for the re oval of sulphur and sulphurous materials om tneoils and distillates. One 'feature of the invention has to do with an improved d'stillation process which is particularly well adapted for the distillation. of oil bearingsan s and similar mineral substances such as oil shale and the like. Another feature of the invention has to do with a distillation process which is particularly well adapted for the recovery of an increased, or

15 exceptionally large, yield of gasoline and other similar distillates, with a minimum amount o f productionof light paratline and olefin gases by cracking.

In order that the\features of the present invention may be better understood and their significancev more' readily appreciated, I will state first that the degree ofheat applied to a composite of oils or to a solid having a potential oil value determines to a large degree the molecular forms vof the distillates. An oil bearing shale, when finely pulverized, is also as susceptible to the action of heat as a composite of oils, and the present process may be applied either to`oi1s I pulverized oil bearing solid-s such as shale. 'f In either case there will be an increase in the production of the lighter hydrocarbon oils as derivatives from heavy pe-. troleum unsaturates, and asphaltic base oils, 3G such .as are often found in shale, sand and peat. The gas formingstages in distillation processes are two in number. First, at low tem-Y perature when the charge is: raised 'grad-` 40 ually to the distilling temperature, the heat is suiicie'nt only totear olf light molecules from the charge and lift them in opposition to thesuper-posed vapor pressure. Second, the second gas forming, or high temperature stage occurs when the heat becomes sufliciently intense to cracku the heavy paratiines by 'tearing olf the terminal carbon atoms of the heavy molecules. These terminal atoms then unite to form the Vlight ethane 3 gas, a paraifine, or saturate, I,

thereforeij' adopt the vplan of feeding the charge, either ulverized shale or oil, slowly into the distillmg mass, which is already at the distilling temperature. .For the prevail- 1923. Serial No. 830,940.

suddenly, in small quantities, into a charge maintained at this temperature, the 'incre- -ment charge is brought instantly to the temperature of themain charge. We know that a pure-gasoline may be raised to`600 C. before the cracking process converts it into light paraiiine and olefin gases. Hence a heat of 400? t'o 450 C. avoids the 10W temperature gas forming stage, while the high gas forming or cracking stage has not been reached. Pulverized solids, as shale for example, can be instantly "brought to this desired temperature in a preheater in which small volumes of the charge canibe easily controlled.` The charge in the preheater lmay be dropped into a dry furnace heat, or

a high boiling Huid previously heated to the desired temperature or superheated steam may be injected into the preheated charge. After the preheating the increment charge may be fed into the general retort charge. In case the process is being ap lied to the distillation 0f oil, said oil may e fed slowly but 'directlyinto the still charge, but preferably forced into the oil below the surface, where it is instantly incorporated intov the hot charge. ,Since this partl of mv process is principally made up of manipulations, any device may be employed which meets the suggested requirements.

The' presence of sulphur in theoil` or derivatives is extremely detrimental from" different standpoints. The sulphur generally-.gives to the oil a detrimental smell or odor, and when the oil is burned, the s111- phur resent passes off as SO2 cfr-,sulphur dioxi e. This sulphur dioxide immediately lassociates itself with any moisture present for the formation of sulphurous acid, HZSOa, and the sulphurousv acid. in turn frequently undergoes changes 4b v- Which it is converted into sulphuric acid 1:12804. Either the sulphurous yor sulphuric acid will react with boilers or ues or other metallic objects with serious corrosion and'l deterioration. R

the oil and its derivatives, I make use of the extremely violent chemical 'aliinity of nascent hydrogen for the sulphur .present in the,- oil and which is to be' eliminated.4

In order to eliminate the sulphur fromv dlature for use in the The nascent hydroUen combines with .the sulphur to form H2 or hydrogen sulphlde. This is agas. t F

`Ordinarys or quiescent hydrogen does not possess afsuiiicient aftinity for the sulphur iin the oils to combinewith it for the purpose of removing it therefrom, and it, therefore, becomes necessary to provide a process and arrangement for generating the nascent hydrogen on the spot and in immediate contact-with the, oil and its sulphur content.- Nascent hydrogen may be produced in quantities by bringing carbon monoxide, CO, into contact with steam, H2O, at a teinper'ature of 400' to 500 C. The vfollowing reaction then takes. place: CO-I-HZOICOZ-l-QIT The instant that the carbon monoxide gas and water are brought' into contact at the proper temperature they will react according to theabove equation and generate the hydrogen. This hydrogen is nascent at the instant of generation, but immediately afterwards becomes quiescent. In order tosecure the beneficial action of the hydrogen on the sul-V phur it therefore becomes necessary to bring about thisreaetion in the immediate pres-lv ence of the oil containing the sulphur. I,

therefore, contemplate the generation of the carbon monoxide and .the steam in separate places, and contemplate bringing them torgether under the desired temperature at the point where he oil to be acted upon is located.

This contemplates bringing the carbon monoxide` and the steam together.

at a temperature of 4006-5000 C. at the point where the. oil or shale is locate The carbon monoxidel may be generated in any suitable manner, but conveniently as producer gas in a gas producer. If this gas producer is equipped for both air and steam blow, `fthe air blow should produce la. gas having substantially a 48% content of carbon monoxide and a substantially equal volume of atmospheric nitrogen. The steam blow should produce a gas which approximates 48% carbon monoxide and 48% hydrogen in place of atmospheric nitrogen. Ineither case, however, the carbon monoxide gaskwill be produced at high temperature, so that it 1 will not be necessary to afterwards 'heat it to the desired temperproduction of the nascent hydrogen in contact with the oil.

The introduction of the hot carbon monoxideI and steam'individually into the shale or the body-of the oil being treated may be done in any convenient" manner, 4as for example by the use of-rabbles such as are disclosed in the BishopOPatent N o. 1,166,175,

In such case a rabble` should be provided with passages for" the independent introduction of the carbon` Vmonoxide and the steam, which passages will be brought close :together at their discharge points, so that L A Y `ter are fully saturated.

which the nascent hydrogen aiseswlrl- 80 hydrogen to produce ygen on the sulphur,

combination with the sulphur; any defio ciency of hydrogen within the oil is made up by the nascent hydrogen, since unsaturated hydrocarbons cannot exist as such when in contact with nascent hydrogen, although the nascent hydrogen is inert as far as the hydrocarbons are-concerned when the lat- The action by the condition of satii sa-turates vto o whence they originated, may be better vi\s-\ ualized by considering the hypothetical molecule of amylene oil. The molecule of amylene oil may be represented as tive four sided polygons each representing an atom of carbon. The adjacent corners of three pairs of these polygons come together, leaving ten exposed points representing ten 4atoms of hydrogen,'and the second and third polygons are brought together by a doublelinkage. Upon saturating this molecule of amylene oil with hydrogen, the double linkage is. broken to expose two additional points between the second and third carbon atoms, thus representing two additional atoms of hydrogen. 'Quiescentl hydrogen does not have sufficient attinity for4 the carlbon to openup the chain between the second lhydrogen into thev body of the oil or into contact with the oil bearing material as is done in my process also results in the conversion` of the f unsaturates into 100% satura-tes with corresponding increase in the commercial value of hydrocarbon oils of saturated purity.

The nascent vhydrogen also has a very.

large affinity for nitrogen, and most mineral oils contain more or less nitrogen in their body. This will combine with .the nascent NH3 or ammonia, by product ,of many the body of scent hydroit is desirable to elimia precipitation process inthe gas to remain in the such. The Co2 gas genprocess of liberating the 1s also an objectionable which .is a valuable distillation processes. After producing the HZS in the material by the action of natethe same by stead of allowing oil or pass off as erated during the nascent hydrogenymaterial within the body undergoing treatr following equatlon ment, Both the' CO2 and I-I2S ma\y\\\b\e\ absorbed by lime, either in the quick or slaked condition, as CaO or Ca(OH)2', with treXtipn of sulphur,

mendous avidity. The introduction of a smal-l quantity of lime into either a solid or liquid oil charge undergoing 'treatment will eliminate both the CO2 and the I-IzS compounds and produce solid calcium compound during the process, which calcium may be easily eliminated by precipitation or otherwise. f

In case any small trace of sulphur should be left in the material, it may be readily rel moved from the vapors by passing them through a screen, scrubber, orother device on which a spray of lead acetate solution is made to flow. v

y Most earths, and minerals such as shale,

4peat andthe like, which are oil bearing,`

contain from small. traces to several per cent of iron in combination. The carbon monoxide, CO, generated in the charge, will react with theqiron oxide according tothe areoioozreaiooz.

' In this way the metallic iron is liberatedby the carbon monoxide.I rIhe hot steam introduced into the charge Willimmediately react with the metallic iron soproduced, according to the following equation:

3Fe-}4H2O:Fe;,0-i-4H2. In this way additional nascent hydrogen'is lmmediately produced and the iron is put Vback into its oxide condition. Thus the iron may travel back and forth between the car,-

bon monoxide and the steam so as to con" stantly `prpduce more nascent hydrogen, thereby assisting the action. When the iron content of the charge is very low or entirely wanting, I recommend that iron ore, ferru- "ginous clays or coal ashes be added in small quantity. i

This action is also assisted or activated by the presence of achloride or an acetate salt. This chlorine 'performs a sort of. intermolecula'r migration-by Starting the initial reaction andn then surrendering its position to oxygen from the steam and then passing on -to another molecule for similar af-tion. The iron! oxide thus formed is then subjected Cto the action of carbon monoxide and reduced to aymetallic state so that it may be acted-upon by the steam t6 generate the nascent hydrogen. l l

If desired, the stirring devices such as rabbles may be made of two different metals, for instance, iron .and copper, whereby the iow of nascent hydrogen may be in creased by electrolytic action attemperaytures ranging from 350 to 450 C.

It willfbe apparent that the generation of nascent hydrogen in difect contact. with the material serves a number of beneficial purposes-including the conversion ,of unsaturated hydrogen into saturatcs, the eliminaand the formation of addiidnal quantities of ammonia, the reducing acti \Nipon oxidized hydrocarbons such as asphalte a .Kthe like It is also evident thatas far as t se beneficial vadvantages are concerned, it isislargely immaterial as to just how the nascent hydrogen is generated provided it is nascent in contact with the mass of material undergoing treatment. In this connection, however, it is very desirable to conduct the treatment by hydrogen at temperatures approximating 40D-500 C., so as to avoid `low Lten'rperature gas'formation, and also to prevent high gas formation or' cracking. Inasmuch as nascent `hydrogen may be directly generated by the contact of steam and carbonmonoxideywithin this range of temperatures itA follows that this particular lmethod 'of generating the nascent hydrogen is extremely desirable the process -With all of the beneficial advan- A tages previously set forth herein.

Normal hydrocarbon oils are saidto be ,ofv paraiiinev base, but paraffine base oils when being exposed to weathering conditions absorb atmcspheric oxygen and thus becomewasphaltic base oils. Now, the' gas carbon monoxide, CO, has Inot only the reducing power to deoxidize water i vapor.

(steam) vand the iron oxides, but it has the power to extract'oxygen from asphaltic oils, when the monoxide gas isin excess of steam. The vasphaltic oil, thus deprived of,4

vits oxygen is ready for hydrogenation by the nascent hydrogen. ABy this process as` .l

phaltic (slop) oils are rejuvenated and thrown back into the paraliine class Whepce they originated.

In the drawing, I have. illustrated dia-` grammatically one arrangement of apparatusfor practicing the features of the prescent invention when shale is to be treated. This illustration is purely diagrammatic and is not intended in -any sense. asa limitation upon the disclosures or prac-- tice of the invention.-

In this case I. have illustrated a''main,

chamber 1 above which isv a preliminary heating chamber 2. The material in the chamber 2 may-'be introducedv .from time to time into the chamber 1 by manipulation of a door 3 between the two chambers.

The raw materialsuch as oil shale is initiallyintroducedy into a feeding chamber 4 by removing the cover 5, and a bell 6 which may be manipulated by 'a lever 7 is nsedto control the intermediate delivery' of the raw material into the chamber 2. v'

A gas producer is illustrated diagram-4 lill matically at 8, the same/delivering the carbon monoxide into thechainber 1 through v'a pipe '9, the inner end of which -is pro-- vided with a number of perforations. The steam may be introduced through a pipe Whose inner end is adjacent to that of the pipe 9 and is also perforated.

A burner 1l serves as a means for heaty ing the chamber 1, andthe finally treated residuuln material may be Withdrawn through a port 12. A connection 13 serves for delivery 'of the vapors.

When lime` or similar material is to be used in connection with the process, the same may 'be introduced from a feeding chamber 14 under control of a bell 15 mat nipuiated by a lever 16.

While I haveherein shownand described only a single apparatus for the practice of the featuresl of the present invention, do

- no intend to limit myself thereto.

I claim: l. The process for the treatment o oil bearing materials for the purpose of saturating with hydrogen their unsaturated hydro-v ently at temperatures of Ll"-500 C. intoI the mass and bringing them into asscialtion at lthe point of introduction into the v mass, to thereby generate nascent hydrogen n reactin at said temperature in the immediate presence ofthe mass, together With liberation of carbon dioxide,said nascenthydrogen with sulphur present in the mass to pr uce hydrogen sulphide, and which consistsr'in introducing lime into the mass,

whereby the lime reacts with the carbon .dioxide and the hydrogen sulphide to produce Ifrelatively heavy'w compounds` insoluble in oil, substantially as described.

2. 'The' process for thel treatment of oil l bearing materials for lthe purpose/of sat= urating with hydrogentheir unsaturated hydrocarbons, eliminating sulphur from them, and converting their nitrogen compounds into ammonia, which consists in instantly ralsing the temperature of saidoil bearin materlals to substantially 4500-500?- thereby eliminating the formation of fixed orl non-condensable gases, thereafter introdependently at temperatures' of 450-500 ducing carbon monoxidegas and steam in- 55 C., into the mass -and bringing them into 'l drocar ons, eliminating sulphur from them,

and converting their nitrogen compounds into ammonia, which consists in introduc ing carbon monoxide gas and steam independently at temperatures of 450-500 C. into the mass and bringing them into association at the point of introduction into the mass, to thereby generate nascent hydrogen at such temperature in the immediate presence of the mass, together With liberation of carbon dioxide, said nascent hydrogen reacting with sulphur present in the=mass to,l produce hydrogen sulphide, and which consists in introducing -lime into the mass, whereby the lime reacts withthe carbon dioxide and the hydrogen sulphide to produce relatively heavy compounds insoluble in oil, substantially as described. 4,.- The process for the treatmentwof oil,.-

bearing materials for the purpose of sat-:fifi

urating With hydrogen their unsaturated hydrocarbons, eliminating sulphur from 90.

them, and converting their nitrogen compounds into ammonia, which consists in introducing carbon monoxide gas and steam -independently at temperatures of `450-500'- C. into the mass and bringing them into association at the point of introduction into lthe mass, to thereby generate nascent hydrogen at such temperature in the immediate presence of the mass, together with liberation of 'carbon dioxide,v said nascent hydrogen reacting with sul. phur present in the mass to produce hydrogen sulphide, substantially as described.

JAMES A. BISHOP- r e f; 

